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Title:
COLORED CONDUCTIVE COATING COMPOSITION
Document Type and Number:
WIPO Patent Application WO/1995/008829
Kind Code:
A1
Abstract:
The present invention is directed to a colored conductive composition comprising a colorant, conductive particles, a resin and optionally, a liquid. There is from about 1 to about 20 %, on the weight of the conductive particles of at least one colorant. A useful composition comprises from about 2 to 20 % by weight of at least one thermoplastic or thermosetting resin. There is about 40 to about 70 % by weight of at least one conductive particle comprising metal or metal compounds, and graphite. Useful article comprises substrates supporting the compositions.

Inventors:
RUSSO FRANK R
ROSE ADRIAN I
Application Number:
PCT/US1994/010293
Publication Date:
March 30, 1995
Filing Date:
September 13, 1994
Export Citation:
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Assignee:
ENGELHARD CORP (US)
International Classes:
C09D5/24; H01B1/22; H01B1/24; (IPC1-7): H01B1/22; C09D5/24; H01B1/20; H01B1/24
Foreign References:
FR2662703A11991-12-06
DE3922499A11991-01-17
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Claims:
What is claimed is:
1. A composition comprising: a) from about.
2. to about 20 percent by weight of at least one resin; b) from about 1 to about 20 percent by weight of at least one colorant; c) from about 40 to about 80 percent by weight of at least one conductive particles selected from metals, metal compounds and graphite; and d) from about 15 to about 50 percent by weight of at least one liquid.
3. 2 The composition as recited in claim 1 wherein the binder is selected from the group consisting of thermosetting resins and thermoplastic resins; the colorant is selected from the group consisting of organic pigments, inorganic pigments and dyes; wherein the conductive metal particles are selected from the group consisting of silver, copper, gold, bronze, tin, platinum, aluminum and wherein the liquid is an organic liquid or water.
4. The composition as recited in claim 2 wherein the resin is selected from the group consisting of polyesters, alkyd resins, acrylic resins, polyvinyl acetate resins, terpene resins, cellulosic resins, epoxy resins, phenolic resins, polyvinyl chlorides, plastisols and styrenic polymers; wherein the colorant is selected from organic pigments and dyes; wherein the conductive metal particles is selected from silver, copper and bronze; and wherein the liquid is selected from the group consisting of alcohols, esters, ethers, ketones, halogenated hydrocarbons, toluene, benzene and xylene.
5. The composition as recited in claim 2 wherein there is from about 5 to about 15 percent by weight of at least one resin.
6. The composition as recited in claim 2 wherein there is from about 3 to about 20 percent by weight of at least one colorant.
7. The composition as recited in claim 5 wherein there is from about 5 to about 15 percent by weight of at least one colorant.
8. The composition as recited in claim 2 wherein there is from about 25 to about 45 percent by weight of at least one liquid.
9. The composition as recited in claim 7 wherein there is from about 35 to about 45 percent by weight of at least one liquid vehicle.
10. The composition as recited in claim 1 wherein there is from about 40 to about 70 percent by weight of at least one conductive particle.
11. The composition as recited in claim 9 wherein there is from about 50 to about 55 percent by weight of at least one conductive particle.
12. The composition as recited in claim 1 wherein the at least one conductive particles have an effective diameter of from 0.1 to 20 micrometers.
13. The composition as recited in claim 11 wherein the at least one conductive particles have an effective diameter of from 0.5 to 10 micrometers.
14. The composition as recited in claim 12 wherein the at least one conductive particles have an effective diameter of from l to 2 micrometers.
15. The composition as recited in claim 11 wherein the at least one conductive particles are in flake form.
16. The composition as recited in claim 14 wherein the at least one conductive particles in flake form are selected from the group consisting of leafing type flakes, non¬ leafing type flakes and mixtures thereof.
17. The composition as recited in claim 15 wherein the at least one conductive particles in flake : orm comprises from 1 to 99 percent by weight leafing type flakes and 99 to 1 percent by weight nonleafing type flakes based on the particles in flake form.
18. The composition as recited in claim 16 wherein the at least one conductive particles in flake form comprises from 10 to 90 percent by weight leafing type flakes and 90 to 10 percent by weight nonleafing type flakes based on the particles in flake form.
19. The composition as recited in claim 17 wherein the at least one conductive particles in flake form comprises from 25 to 75 percent by weight leafing type flakes and 75 to 25 percent by weight nonleafing type flakes based on the particles in flake form.
20. The composition as recited in claim 18 wherein the at least one conductive particles in flake form comprises from 40 to 60 percent by weight leafing type flakes and 60 to 40 percent by weight nonleafing type flakes based on the particles in flake form.
21. A composition comprising: a) from about 2 to about 25 percent by weight at least one resin; b) from about 1 to about 35 percent by weight of at least one colorant; and c) from about 45 to about 85 percent by weight of at least one conductive particles selected from metals, metal compounds and graphite.
22. The composition as recited in claim 20 wherein the resin is selected from the group consisting of thermosetting resins and thermoplastic resins; the colorant is selected from the group consisting of organic pigments, inorganic pigments and dyes; and wherein the conductive metal particles are selected from the group consisting of silver, copper, gold, bronze, tin, platinum, aluminum.
23. The composition as recited in claim 21 wherein the resin is selected from the group consisting of polyesters, alkyd resins, acrylic resins, polyvinyl acetate resins, terpene resins, cellulosic resins, epoxy resins, phenolic resins, polyvinyl chlorides, plastisols and styrenic polymers; and wherein the colorant is selected from organic pigments and dyes; wherein the conductive metal particles is selected from silver, copper and bronze.
24. The composition as recited in claim 20 wherein the at least one conductive particles have an effective diameter of from 0.1 to 20 micrometers.
25. The composition as recited in claim 23 wherein the at least one conductive particles have an effective diameter of from 0.5 to 10 micrometers.
26. The composition as recited in claim 24 wherein the at least one conductive particles have an effective diameter of from 1 to 2 micrometers.
27. The composition as recited in claim 23 wherein the at least one conductive particles are in flake form.
28. The composition as recited in claim 26 wherein the at least one conductive particles in flake form are selected from the group consisting of leafing type flakes, non¬ leafing type flakes and mixtures thereof.
29. The composition as recited in claim 27 wherein the at least one conductive particles in flake form comprises from 1 to 99 percent by weight leafing type flakes and 99 to 1 percent by weight nonleafing type flakes based on the particles in flake form.
30. The composition as recited in claim 28 wherein the at least one conductive particles in flake form comprises from 10 to 90 percent by weight leafing type flakes and 90 to 10 percent by weight nonleafing type flakes based on the particles in flake form.
31. The composition as recited in claim 29 wherein the at least one conductive particles in flake form comprises from 25 to 75 percent by weight leafing type flakes and 75 to 25 percent by weight nonleafing type flakes based on the particles in flake form.
32. The composition as recited in claim 30 wherein the at least one conductive particles in flake form comprises from 40 to 60 percent by weight leafing type flakes and 60 to 40 percent by weight nonleafing type flakes based on the particles in flake form.
33. The composition as recited in claim 20 comprising from 65 to 75 percent by weight of the at least one conductive particles.
34. An article of manufacture comprising: a substrate; and a composition supported on the substrate, wherein the composition comprises: a) from about 2 to about 20 percent by weight of at least one resin; b) from about 1 to about 20 percent by weight of at least one colorant; c) from about 40 to about 80 percent by weight of at least one conductive particles selected from metals, metal compounds and graphite; and d) from about 15 to about 50 percent by weight of at least one liquid.
35. The article as recited in claim 33 wherein the resin is selected from the group consisting of thermosetting resins and thermoplastic resins; the colorant is selected from the group consisting of organic pigments, inorganic pigments and dyes; wherein the conductive metal particles are selected from the group consisting of silver, copper, gold, bronze, tin, platinum, aluminum and wherein the liquid is an organic liquid or water.
36. The article as recited in claim 34 wherein the at least one conductive particles have an effective diameter of from 0.1 to 20 micrometers.
37. The article as recited in claim 35 wherein the at least one conductive particles are in flake form.
38. The article as recited in claim 36 wherein the at least one conductive particles in flake form are selected from the group consisting of leafing type flakes, non¬ leafing type flakes and mixtures thereof.
39. The article as recited in claim 33 wherein the liquid has been removed.
40. The article as recited in claim 38 wherein the composition comprises: a) from about 2 to about 25 percent by weight at least one resin; b) from about 1 to about 35 percent by weight of at least one colorant; and c) from about 45 to about 85 percent by weight of at least one conductive particles selected from metals, metal compounds and graphite.
41. A method comprising the step of conducting an electric current through a layer of coating composition supported on a nonconducting substrate wherein the coating composition comprises: a) from about 2 to about 25 percent by weight at least one resin; b) from about 1 to about 35 percent by weight of at least one colorant; and c) from about 45 to about 85 percent by weight of at least one conductive particles selected from metals, metal compounds and graphite.
Description:
COLORED CONDUCTIVE COATING COMPOSITION BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to an electrically conductive coating composition comprising a colorant. More particularly, the invention relates to a conductive composition comprising a colorant which can be a pigment or dye.

Prior Art

US Patent No. 5,006,278 discloses an electrically conductive substituted and unsubstituted polyaniline composition having different colors. The composition can also include various conductive polymers, graphite and metal conductors. A polar organic solvent is disclosed for use to form a coating for conductive articles. Other components can include conventional polymers, fillers and the like. The polymer can be used as a coating or in the form of fibers and films of any desired thickness. Conductive coating materials comprising vinyl resin, carbon black, conductive metal containing powder, epoxy compounds and/or organic stabilizers that can be colored into different colors are disclosed or as is for example to US Patent Nos. 5,006,278; 5,066,422 and 4,079,156. US Patent No. 4,079,156 discloses conductive metal pigments which are useful in electrical devices.

US Patent No. 4,529,539 discloses electrically conductive high molecular weight compositions obtained by

mixing high molecular weight compounds such as thermoplastic resin, synthetic resin, a rubber or the like with a water soluble electrolyte and a water soluble high molecular weight compound. The electrolyte is a soluble salt which can include sodium, potassium chloride or sulfite, carbonate, phosphate, thiocyanate and the like. The conductive high molecular weight composition can be transparent and colored to any desirable color. The compounding ratio of the water soluble electrolyte and the water soluble high molecular weight compound respectively per hundred parts of the base high molecular weight compound is from 1 to 10 parts by weight. The composition does not contain either carbon black or metallic powder. It can be colored to any desirable color by adding a colorant useful for ordinary thermoplastic resins or rubbers.

US Patent No. 4,052,256 and Reissue Patent No. 33,285 disclose articles having a transparent conductive polymeric coating body resistance to close a circuit. Such articles include watches and lamps. Conductive polymeric compositions are also disclosed in US Patent Nos. 4,264,477 and 4,518,833.

While colored conductive coating compositions are known, such compositions are primarily compositions which are made of conductive polymers which can be colored. Alternatively, the conductive particles are colored, or maintain the color inherent in the color of the particles such as the silvery color of silver or aluminum or the natural colors of copper, bronze, gold or the like.

Conductive coatings have been colored black using carbon black.

Summary of the Invention

The present invention is directed to a colored conductive composition comprising a colorant, conductive particles, a resin which can function as a binder, and optionally, a liquid which can be an organic liquid or water. There is from about 1 to about 20%, preferably 3 to 20%, and more preferably 5 to 15% based on the weight of the conductive particles of at least one colorant. The colorant can be a dye or a pigment and provide a color in the range from violet to red. This includes all of the colors that are in the visual light wave length band including white. A useful composition comprises from about 2 to 20% and preferably 5 to about 15% by weight of at least one binder. The binder is preferably a resin which can be a thermoplastic or thermosetting resin. There is about 40 to about 80% by weight and preferably 50 to 55% by weight of at least one conductive particle comprising metal or metal compounds, and graphite. Preferred metals or metal compounds include but are not limited to silver, gold, platinum, palladium, copper, brass, bronze, and aluminum. Preferred metal compounds include but are not limited to metal sulfides, carbides, carbonyls and nitrides. The preferred composition useful for a coating further comprises from 15 to 50, preferably 25 to 45 and more preferably from 35 to 45% by weight of a liquid vehicle.

Preferably, the liquid vehicle is selected from an organic solvent or water. Depending on the amount and type of colorant and resin, the composition can be a non-self- supported coating or a self supporting film, fiber or molding or the like. The composition without the liquid comprises from about 5 to about 20 percent by weight of at least one resin; from about 3 to about 20 percent by weight of at least one colorant; and from about 40 to about 70 percent by weight of at least one conductive particle selected from metals, metal compounds and graphite.

The present invention includes articles of manufacture comprising coating compositions as recited. The liquid can be removed by any suitable means leaving a conductive coating on the article. Articles include textiles, film sheets, fibers and particles which support the coating.

The present invention further includes a method comprising a step of conducting an electric current through a layer of coating composition supported on a non¬ conducting substrate wherein the coating composition comprises the composition as recited wherein the liquid has been removed.

Brief Description of the Drawings

Figure 1 shows an article which includes the conductive coating composition of the present invention. Figure 2 shows a typical silk screen testing sample of conductive composition of the type made using Example 28-35

composi .ti.ons, on Mylar® polyethylene terephthalate film.

Detailed Description of the Preferred Embodiments

The present invention will be understood by those skilled in the art based on the following description and further in view of Figure l. A preferred coating composition of the present invention comprises from about 5 to about 20, preferably 5 to 15 and more preferably 9 to 12% by weight of at least one resin; from about 3 to about 15% by weight of at least one colorant; from about 40 to about 70 and preferably 50 to 55% by weight of at least one conductive particle comprising metals or metal compounds in graphite, and from 25 to 45 and preferably 35 to 45 of at least one liquid vehicle.

In a composition not including the liquid, but including a coating, film or self-support articles comprises from about 5 to about 20, preferably 9 to 12% by weight of at least one resin; from about 3 to about 20 and preferably 5 to 10% by weight of at least one colorant; and from about 40 to about 70, and preferably 50 to about 55% by weight of at least one conductive particle comprising metals or metal compounds and graphite.

The conductive particles can include metals including pure metals and metal alloys. Useful metals include silver, iron, copper, brass, gold, platinum, silver alloys, gold alloys, bronze, aluminum, nickel and copper, as well as metal coated non-conducting particle such as metal coated glass. Useful conductive metals and metal pigments are disclosed in US Patent No. 4,079,156 hereby incorporated by

reference. Conductive metal pigments include the alloy of a non-noble conductive metal with at least one oxidizable metal selected from the group consisting of carbon, boron, silicon, aluminum, carbon-silica, and boron-silicon and nickel carbonyl. The metal compounds can additionally include organo etalics such as metallocenes such iron carbonyl, also useful are graphite and carbon black particles.

The particles should have a morphology that permits electrical conductivity. Useful particles can be spherical, flat, irregularly shaped or coated with the composition as recited above. Preferably, pure metals are flake or flat- like in shape. The preferred particles are flakes which have an aspect ratio of less than 20 and preferably 10 to 20, with a thickness of less than 1 micrometer (μ) . Other useful particles have an effective spherical diameter range of from 0.1 μ to 20 μ and preferably 0.5 to 10 μ . The effective diameter is the diameter of a sphere having the same volume as the particle. The metals and conductive materials are typically characterized as having an average effective diameter of 1 to 2 μ .

Preferred particles are in flake form with silver flakes being most preferred. Silver flakes can be a leafing or nonleafing type. In compositions of the present invention leafing-type silver flakes are believed to align with the coating. A surface or plane of the coating is generally parallel to the major plane of the silver flakes. The major plane through nonleafing silver plates are

believed to be randomly oriented in the coating. Useful leafing type silver flakes have particle sizes ranging from 1-15 μm determined by scanning electron micrographs. Apparent density ranges from 16.0-32.0 g/in 2 measuring using a Scott Volumeter, per ASTM B329-81. Tap density ranges from 2.0 to 3.0 measured using a Tap-Pak Volumeter, per ASTM B527-81. Weight loss (%) at 110°C is about 0.10 and at 538°C about 0.85 to 0.90 maximum. Useful nonleafing silver flakes have particle sizes ranging from 0.5-10 μm determined by scanning electron micrographs. Apparent density ranges from 20.0-40 g/in 3 measured using a Scott Volumeter, per ASTM B329-81. Tap density ranges from 2.5 to 4.5 measured using a Tap-Pak Volumeter, per ASTM B527-81. Weight loss (%) at 100°C is about 0.10 and at 538°C about 0.65 to 0.90 maximum. Nonleafing impurities having a maximum of from 0.002 to 0.004% (Na + K) and 0.001 to 0.002 (CD .

It is recognized that certain metals such as silver, when formed into flat or flake-like particles also include a sufficient amount of lubricant such as an organic soap which can be oleic, stearic, lauric or acid or salt thereof to prevent agglomeration of the flakes during processing. Typically, there is from 0.5 to 2% by weight of the organic soap in the flake-like materials. It has been found that the use leafing type and nonleafing type flake particles affects color intensity and composition resistivity. Compositions using leafing metal flake result in light, pale color appearance with lower

resistivity. Compositions with a mixture of leafing and non-leafing metal flake result in bright color appearance and relatively low resistivity. Particular color quality and intensity and compositions can comprise a mixture of flake leafing and nonleafing metal particles in the following weight percent ranges (based on the leafing and nonleafing particles) of leafing range to nonleafing range particles: 1-99 to 99-1, 10-90 to 90-10, 25-75 to 75-25 and 40-60 to 60-40 weight percent. A colorant is a substance that imparts color to another material. Colorants are either dyes or pigments. A colorant may either be naturally present, admixed with a material such as dried pigments and paints or applied in solution such as organic dyes. Typically, a distinction between dyes and pigments is difficult to draw. However, most pigments are considered to be insoluble dry powders. Such powders are insoluble in both water and organic solvents. The coloring effect of a pigment is considered to be the result of their dispersion in a solid or liquid medium. Dyes on the other hand are soluble, synthetic organic products which are chemically bound to and actually become part of the material to which they are applied. Instruments for measuring, comparing and matching the hue, tone and depth of color are called colorometers. Pigments are useful as colorants in a composition of the present invention. Typically useful pigments for the present invention include inorganic pigments such as metal oxides, including iron, titanium, zinc, cobalt and chromium

oxides. Also included are metal powders suspension. Earth color pigments are provided as siennas, ocras, and umbras. Finally, lead based pigments such as lead chromates can be used. Organic pigments include animal-based compounds, including rhodopsin and melanin. Organic vegetable derived pigments include chlorophyll, xanthophyll, litmus, flavon, and carotene. Mineral pigments and finally synthetic pigments such as phthalocyanin, lithols, toluidine, para red toners, lakes and the like. Useful pigments are set forth in the Condensed Chemical Dictionary, Eighth Edition, Van Nostrand Rheinhold, p. 695 hereby incorporated by reference.

The Condensed Chemical Dictionary, supra, p. 338, hereby incorporated by reference, lists useful dyes which can be used with the present invention. Included in these dyes are metal dyes, natural dyes, synthetic dyes, and dispersed dyes. Metal dyes are organic dyes suitable for use with a metal such as aluminum or steel. Such dyes include alizarin cyanin RR, alizarin green S, nigrosine 2Y and naphthalene blue RS. Natural dyes are obtained from natural animal or tree sources. Among the best known are madder, cochineal, logwood and indigo.

Synthetic organic dyes are often derived from coal, tar and petroleum based intermediates. Dyes may either by acidic or basic and their effectiveness on the objects to be dyed may depend on this factor. Some dyes are soluble in water while others are soluble in organics. Synthetic dyes include acetate dyes, anthraquinone dye, acid dye, azo dye,

alizarine analyn, eosin, stilbene dye and sulfide dye. Dispersed dyes fall into three defined chemical classes including nitrorylamine, azo and anthraquinone and almost all contain amino or substitute amino groups but not solubilizing sulfonic groups.

Useful colorants include various classes of dispersed dyes such as nitro dyes, amino ketone dyes, ketone-imine dyes, methine dyes, nitro diphenyl amine dyes, quinoline dyes, amino naphthoquinone dyes, coumarin dyes and anthraquinone dyes as well as azo dyes such as monoazo dye, disazo dyes. Other dyes include indigoid dyes, anthraquinoid dyes for example indianthrene and also sulfur dyes. Other useful dyes are listed in Webster's Third New International Dictionary of the English Language. Unabridged. pp. 706-710 (1986) .

Pigments are defined at Webster's, supra, page 1714, also incorporated herein by reference.

The composition including the colorant and conductive compound are held together by a binder composition, preferably comprising a polymeric binder which can be a thermoplastic or thermosetting polymer. The resin is preferably chosen so that if the composition is to be used to cost a substrate, the resin adheres to the substrate. For example, a polyester binder can be used with a polyester (Mylar ) substrate.

Useful thermoplastic polymers include but are not limited to polyethylene, polypropylene, polystyrene, polybutadiene, polyvinyl acetate, methacrylate resin, AS

resin, ABS resin, AAS resin, ACS resin, AES resin, polyacetal, polyamide, polyphenylene oxide, polycarbonate, linear polyester, polyurethane, polyvinyl alcohol, ethylene vinyl alcohol copolymer, chlorinated polyethylene, chlorosulfonated polyethylene, polyisoprenes, chlorinated rubber, rubber hydrochloride, styrene butadiene rubber, polyacrylonitrile, polymethylmethacrylate, polymethylacrylate, polyacrylic acid, polymethycrylic acid, ethylene acrylic acid copolymer, ethylene methycrylic acid copolymer and salts thereof, methylcyanoacrylate monomer, polyacrylamide, copolymers of styrene and methylmethacrylate, rigid polyvinyl chloride, copolymers of polyvinyl chloride, elasticized polyvinyl chloride and vinyl chloride copolymers, plastisols and organisols, polyoxyethylene, polyglycols, polysulfides, polyeptides, cellulosic polymers, or the like. The thermoplastic polymer include both homopolymers or copolymers. Other useful polymers include fluorinated polymers such as polyvinyl fluoride, polyvinylidine fluoride, polychlorotrifluoroethylene copolymer, polytetrafluoro- ethylene, polyvinylidine fluoride and fluorinated ethylene propylene copolymers. Useful linear saturated polyesters include polyethyleneterephthalate and polybutyleneterephthalate. Useful ionic copolymers include the salts of copolymers of ethylene and an alpha beta ethylinically unsaturated carboxylic acid including copolymers of ethylene and salts of acrylic or methacrylic acid. The salts can include the Groups I and II metal salts

with sodium, potassium, zinc and magnesium being preferred. Polyamides include nylon 6, nylon 66, nylon 610, nylon 11, nylon 12 and polyamide copolymers. Useful thermoplastic polymers for the present invention are disclosed in Bilmeyer, Jr. , Textbook of Polymer Science. Second Edition, Wiley into Science, pp. 379 to 462, p. 171 are hereby incorporated herein by reference.

Useful thermosetting resins include but are not limited to epoxy resins such as disclosed in Modern Plastics Encyclopedia. 1979-1980, Vol. 56, No. 10A at page 16-26 hereby incorporated by reference. Useful thermosetting resins also include thermosetting polyamides and thermosetting resins set forth in Bilmeyer, supra, page 468-487 hereby incorporated by reference. Other useful resins include phenolic resins, including phenylphemaldehyde resins, amino resins, terpene resins, unsaturated polyester resins, including the product of dibasic acids such as phthalic anhydride, adipic acid, azelaic acid or isophthalic acid and a dihydric alcohol such as ethylene or propylene glycol, 1,3- and 2,3- butylene, diethylene and dipropylene glycols. Also useful in forming reinforced thermosetting polyester systems are styrenic polymers including styrene, vinyl toluene, methylmethacrylate, diallyl phthalate and triallyl cyanurate. Epoxy resins, with a commonly used epoxy resin made by condensing an epoxy such as epichlorohydrin and an hydroxyl group containing compound such as bisphenol A,

(diphenylol propane) , resorcinol, hydroquinone, glycols and

glycerol. Also useful are polyurethanes and thermosetting silicone polymers, alkyd resins, allyl resins, furane resins and thermal setting acrylic resins.

Useful liquids include water wherein the composition is an aqueous solution dispersion or latex and organic liquids. Useful organic liquids include a polar and nonpolar organic solvents. Useful organic liquids depend on the resin and include alkanes, alkenes, aromatics, alcohols, ethers, acetones, ketones, halogenated hydrocarbons, acids, esters, monomeric epoxies, alcohol/ester and aromatics including toluene, benzene, xylene and organic salts. Where the vehicle is a solvent, useful solvents are disclosed in Doolittle, The Technology of Solvents and Plasticizers. J. Wiley & Sons, 1954. Illustrative of useful polar solvents are alkyl alkanesulfonates such as methyl methanesulfonate, ethyl methanesulfonate, butyl methanesulfonate, propyl ethanesulfonate; nitriles such as acetonitrile, propionitrile, butyronitrile, benzonitrile and the like; aromatic solvents such as nitrobenzene and the like; carbonates such as propylene carbonate, dimethyl carbonate, ethylene carbonate and the like; nitroalkanes, such as nitromethane, nitroethane, nitropropane, and the like; amides such as dimethyl forma idedimethyl thioformamide, N,N-dimethylacetamide, N-methylpyrrolidinone and the like; organophosphorus compounds such as hexamethyl phosphoroamide, diethylphosphate, triethylphosphites, trimethylphosphate and the like; and organosulfur compounds

such as sulfolane, methylsulfolane, dimethylsulfone, dimethyl sulfoxide, glycol sulfite, tetraethylsulfamide, aromatic alcohols, and the like. Mixtures of such organic solvents can also be used as for example, mixtures of sulfolane and acetronitrile. Preferred solvents include xylene, benzyl alcohol, dibasic ester and glycol acetates. The composition of the present invention useful for coating is in the form of a liquid suspension of the conductive particles. The suspension is in a solution, suspension or latex of resin with colorant. Where the colorant is in solution, it is considered a dye and where the colorant is in suspension or slurried, it is considered to be a pigment.

The composition can contain other additives such as suspending agents, light and/or heat stabilizers, flow control agents, fibrous and particulate fillers, reinforcing agents, polymeric nucleation agents, platicizers and impact modifiers and the like so long as the conductivity of the coating composition is maintained in a useful range.

The conductivity of the composition of the present invention is determined based on the coating composition after removal of the liquid vehicle. The electric properties of the composition are characterized by sheet resistivity as follows: 0.1 to 10,000 ohms/square, and preferably 0.2 to 1000 ohms/square. Resistivity is defined in Del Toro, Principles of Electrical Engineering, pp. 14,77 Prentice-Hill Inc. (1965). In the case where a

conductor has uniform cross-sectional areas where I is current flow (amps) , Vis

I = A V

P the potential difference is volts across the conductor of length L, A is the cross sectional area, R is the resistance in ohms and p is a property of the material called the resistivity (ohm-meters) . Since V=IR, p=(AR)/(L) (ohm meters). For a flat sheet of uniform thickness (t) and width (w) , p= [ (tw)/(L) ] -R. The number of sheet area units is (L) / (w)=number of squares or unit squares and p=(R) / (unit square) (t) . Where the sheet thickness is uniform the p is measured as ohms per square. The p can be normalized by dividing by the sheet thickness. Depending on the polymer used, as well as the type and amount of colorant and resin, the composition can be a non- self-supporting composition useful as a coating onto a substrate. Alternatively, the composition can be formed into a self supporting structure and formed into films, fibers and formed articles (moldings extrusions) .

The composition of the present invention can be coated by suitable means. Such means include the use of brushes, rollers and printing. A preferred method of coating is by silk screen printing. Coatings can be from at least about 5 micrometers thick with useful coatings being from 5 to 100, preferably 5 to 50, more preferably 5 to 25 and most preferably 5 to 15 μ in thickness. At least part of the conductive coating is in the shape of lines from 0.01 to

0.25, and preferably 0.025 to 0.1 inches wide.

The present invention includes an article coated with the composition. The composition can be set out in a pattern as shown in the accompanying figure. The accompanying figure is an article of clothing such as a T- shirt 10. The article can have thereon a drawing and/or artwork woven, or dyed, or silk-screened onto the article. As part of the article, there can be one or more conducting channels such as 14 and 16 of the coating of the present invention. The coated channels can be coated directly onto the article such as an article of clothing or coated onto a coating already present on the article. The subcoating is useful to prevent the conductive coating from being absorbed into the textile fibers. Referring to the figure, there can be an energy source such as battery 18 having terminals 20 and 22. A conducting means such as a strip of conducting coating or conducting wire 24 is connected from terminal 20 to coated channel 14. Coated channel 14 can be connected to a light such as an LCD 26 which in turn is shown connected to a second LCD light 28 via conductor 30. Light 28 is connected to channel 16 which is connected to terminal 22 of battery 18 through conductor 32. Upon closing of the circuit at the batter, a closed circuit is made and the lights 26 and 28 are turned on. The present invention also includes a method. The method comprises a step of conducting an electric current through a layer of coating composition supported on a non¬ conducting substrate wherein the coating composition

comprises the above-recited composition. More specifically, the method comprises coating a non-conducting substrate with a coating composition of the present invention, removing the liquid vehicle and conducting an electric current through the coating composition. In this case the composition can be formed into film, fiber, molded or extruded by conventional means.

EXAMPLES

Several examples are set forth to illustrate the nature of the invention and the manner of carrying it out. However, the invention should not be considered as being limited to the details thereof.

In the following examples, the conductive materials was silver flake produced by Handy & Harmon, Chemical Products Center, 1770 Kings Highway, Fairfield, CT 06430 and described in the brochure Silflake ® Silver Flakes, hereby incorporated by reference. In particular, silver flake sold as Silflake ® 135 and 237 were used in the following examples. Silflake ® 135, referred to as Type 1, is a leafing-type silver flake and Silflake ® 237, referred to as Type 2, is a nonleafing-type silver flake particle. The reported characteristics of these particles are summarized in Table 1.

TABLE 1

Particle Apparent Tap Dens. 3 Weight Loss*(%) Sz^um. Density 2 (α/m 3 . (g/cm 3 ) 110°C 538°C

Type 1 2-15 16.0-28.0 2.0-3.0 0.10 0.90 Type 2 0.5-10 20.0-36.0 2.5-4.0 0.10 0.65

1 Scanning Electron Micrograph (typical range)

2 Scott Volumeter (ASTM B329-81)

3 τap-Pak Volumeter (ASTM B527-81)

4 Maximum The Type 2 is also characterized as having "low ionic impurities, a maximum of 0.004% (Na + K) and 0.001% (Cl) .

The colorants used included those listed from the Hoechst Celanese Co., Hostaperm Series; and the Sandoz Chemical Corporation, Savinyl Series. The resin used was a thermoplastic copolyester resin and the vehicle was dibasic ester solvent substantially comprising glutaric and tartaric acid. The thermoplastic copolyester is sold by the Goodyear Tire and Rubber Company of Akron, Ohio as Vitel ® 2200. Vitel ® 2200 is reported to have a specific gravity of 1.27, an acid number of from 1 to 3, a hydroxyl number of from 3 to 5, a Tg at onset of 63°C, Tg at nflection of 66°C, a melt flow point of 156°C (ASTM E 28-67) , a tensile at break of 7400 pr and an elongation of 3% (modified ASTM-822A) using an Instron 4200 at 73.4 „ι 3.6°F and a humidity of 50% + 5% with a cross level speed of 0.5 inches/minute, a Shore hardness at 74°F of 74D (ASTM-D2240- 81), a number average molecular weight of 32,000, a weight average molecular weight of 58,000 and a polydispersity (AR-949 Polystyrene Reference) of 1.82. The compositions used contained 50 parts by weight of the silver flake, 10 parts by weight of the colored pigment, 12 parts by wei ~t of the copolyester and 28 parts by weight of the solvent.

The example compositions were pr- red in accordance with the following procedures at ambient temperatures and pressure. The conductive material, colorant, resin and vehicle were mixed in a bowl to form a paste. In Examples 1-27, 10 gram batches were mixed and

dispersed using Hoover-Muller rotating glass plates; larger batches of lOOg of paste for Examples 28-36 were dispersed on a three-roll paint mill where it was ground to a fineness of 3 micrometers or less. The paste was applied to a clear Mylar ® polyester film 5 mils thick. The paste was applied to the film by silk screen printing using a 150 mesh polyester screen to form a 3 inch square. A serpentine pattern was formed 64 inches long by 0.025 inches wide (2560 squares) using the coating composition of Examples 1-27, and a serpentine pattern found 64 long by 0.04 inches wide (1566 squares) was formed using the coating compositions of Examples 28-35. The coating on the film was then dried in a static oven at 100°C for ten minutes. A silk screen sample pattern of the type made using the compositions of Examples 25-35 is shown in Figure 2. Sheet resistivity was measured using a digital multi- ohm meter and the units of resistivity were ohms per square. EXAMPLES 1-9

Example 1 - 9 compositions were made using only silver flake Type 2 (non-leafing) . The results are summarized in Table 1 below:

TABLE 1

EX. COLORANT CURED COLOR OHM/SO.

1. Hostaperm Red FGR Dull Red

0.5

2. Savinyl Orange RLS Dull Orange >1000

3. Hostaperm Orange Dull Lt. Orange 3

4. Hostaperm Brown HFR Dull Brown 1

5. Savinyl Yellow RLSN Dull Yellow >1000

6. Savinyl Green GLS Dull Green 15

7. Savinyl Blue GLS Dull Blue 100

8. Hostaperm Vat Red Dull Purple 1

9. Savinyl Violet Dull Violet >1000

Examples 10-18

Examples 10 - 18 compositions were made using silver flake Type 1 (leafing type) at 25 parts by weight, silver flake Type 2 (non-leafing type) at 25 parts by weight. Table 2 summarizes the results using various colorants.

TABLE 2

EX. COLORANT CURED COLOR OHM/SO.

10. Hostaperm Red FGR Bright Red 0.2 11. Savinyl Orange Bright Orange 13

12. Hostaperm Orange Bright Orange 1

13. Hostaperm Brown Bright Brown 1

14. Savinyl Yellow Bright Yellow 0.3

15. Savinyl Green Bright Green 3 16. Savinyl Blue Bright Blue 5

17. Hostaperm Vat Red Bright Purple 1

18. Savinyl Violet Bright Violet 3

Examples 19-27

Example 19 - 27 compositions were made using silver flake Type 1 (leafing type) . The colorants used and the results are summarized in Table 3 below:

TABLE 3

EX. COLORANT CURED COLOR OHM/SO.

19. Hostaperm Red FGR Pale Red 0.5

20. Savinyl Orange Pale Orange 0.5

21. Hostaperm Orange Pale Orange 0.5

22. Hostaperm Brown Pale Brown 1.0

23. Savinyl Yellow Pale Yellow 5

24. Savinyl Green Pale Green 1.5

25. Savinyl Blue Pa3e Blue 3

26. Hostaperm Vat Red Pale Purple 2

27. Savinyl Dark Violet Pale Violet 4

Examples 28-35

Example 28-35 compositions were made by mixing the 25 parts of silver flake Type 1, 25 parts of silver flakes Type 2, 10 parts of the listed colorant, 12 parts of the copolyester and 28 parts of the dibasic solvent as recited. The resin and solvent were premixed and comprise a vehicle for the metal particles and colorant. The compositions were dispersed on the three roll mill. The colorants treated in Table 4 were Hostoperm ® colored pigments sold by Hoechst. The composition was silk screen printed through a 325 mesh stainless steel stencil screen. The pattern was a 0.040 inch wide by 64 inch long serpentine line (Figure 2) resulting in about 1566 squares. The prints were heated on the 5 mil Mylar ® film at 100°C for 10 minutes. The coating thickness micrometers (μ) was measured using a stylus profilo eter. The colorants and results are summarized in Table 4 below:

TABLE 4

VISCOSITY P THICKNESS

EX. COLOR (KCPS. ohms/sq/ U Sp.Gr

28 Monoazo Red 100 0.23 1. 0 1.915

29 Monoazo Brown 92 0.20 15 1.932

30 Naphthalene 95 0.21 11 2.016 Tetracarboxylic Acid Orange

31 Diazo Yellow 42 0.65 10 1.991

32 Monoazo Yellow 40 0.45 11 3.207

33 Copper Phthalo 95 0.33 12 1.938 Cyanine Green

34 Copper Phthalo 100 0.39 8 1.938 Cyanine Blue

25 Dioxazine Violet 48 0.22 8 1.938

While exemplary embodiments of the invention have been described, the true scope of the invention is to be determined from the following claims: